High charge density metallophosphate molecular sieves

ABSTRACT

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-17 has been synthesized. These metallophosphates are represented by the empirical formula of: 
       R p+   r A m   + M x E y PO z    
     where A is an alkali metal such as potassium, R is a quaternary ammonium cation such as ethyltrimethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-17 family of molecular sieves are stabilized by combinations of alkali and organoammonium cations, enabling unique metalloalumino(gallo)phosphate compositions and exhibit the BPH topology. The PST-17 family of molecular sieves has catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of copending InternationalApplication No. PCT/US2017/033749 filed May 22, 2017, which applicationclaims priority from U.S. Provisional Application No. 62/341,172 filedMay 25, 2016, now expired, the contents of which cited applications arehereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to a family of charged metallophosphate-basedmolecular sieves designated PST-17. They are represented by theempirical formula of:

R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z)

where A is an alkali metal such as potassium, R is at least onequaternary organoammonium cation such as ethyltrimethylammonium, M is adivalent metal such as zinc and E is a trivalent framework element suchas aluminum or gallium. The PST-17 family of materials has the BPHtopology.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing [AlO_(4/2)]⁻ andSiO_(4/2) tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents (SDAs) such asalkali metals, alkaline earth metals, amines, or organoammonium cations.The structure directing agents reside in the pores of the zeolite andare largely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces of the zeolite as well as on internal surfaces within the poresof the zeolite.

In 1982, Wilson et al. developed aluminophosphate molecular sieves, theso-called AlPOs, which are microporous materials that have many of thesame properties of zeolites, but are silica free, composed of[AlO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedra (see U.S. Pat. No. 4,319,440).Subsequently, charge was introduced to the neutral aluminophosphateframeworks via the substitution of SiO_(4/2) tetrahedra for [PO_(4/2)]⁺tetrahedra to produce the SAPO molecular sieves (see U.S. Pat. No.4,440,871). Another way to introduce framework charge to neutralaluminophosphates is to substitute [M²⁺O_(4/2)]²⁻ tetrahedra for[AlO_(4/2)]⁻ tetrahedra, which yield the MeAPO molecular sieves (seeU.S. Pat. No. 4,567,029). It is furthermore possible to introduceframework charge on AlPO-based molecular sieves via the introductionboth of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ tetrahedra to the framework, givingMeAPSO molecular sieves (see U.S. Pat. No. 4,973,785).

In the early 1990's, high charge density molecular sieves, similar tothe MeAPOs but without the Al, were developed by Bedard (see U.S. Pat.No. 5,126,120) and Gier (see U.S. Pat. No. 5,152,972). These metalphosphates (sometimes arsenates, vanadates) were based on M²⁺ (M═Zn,Co), the general formula of which, in terms of the T-atoms, T²⁺-T⁵⁺, wasapproximately Al⁺T²⁺T⁵⁺O₄, having framework charge densities similar toSi/Al=1 zeolites and were charge balanced by alkali cations, A⁺, in thepores. Later attempts to prepare metallophosphates of similarcompositions but with organic SDAs led to porous, but interruptedstructures, i.e., the structures contained terminal P—O—H and Zn—N bonds(see J. MATER. CHEM., 1992, 2(11), 1127-1134). Attempts at Alsubstitution in a zincophosphate network was carried out in the presenceof both alkali and organoammonium agents, specifically the most highlycharged organoammonium species, tetramethylammonium, but because of thehigh framework charge density, only the alkali made it into the pores tobalance framework charge (see U.S. Pat. No. 5,302,362). Similarly, in ahigh charge density zincophosphate system that yielded the zincphosphate analog of zeolite X, the synthesis in the presence of Na⁺ andTMA⁺ yielded a product that contained considerably less TMA⁺ than Na⁺(see CHEM. MATER., 1991, 3, 27-29).

To bridge the rather large charge density gap between the MeAPOs of U.S.Pat. No. 4,567,029 and the aforementioned alkali-stabilizedMe²⁺-phosphates of Bedard and Gier, Stucky's group developed a synthesisroute using amines, often diamines in ethylene glycol-based reactionmixtures. They were able to make high charge density, small pore MeAPOsin which the concentrations of Co²⁺ and Al³⁺ in R(Co_(x)Al_(1-x))PO₄were varied such that 0.33≤x≤0.9 in the so-called ACP series ofmaterials, the aluminum cobalt phosphates (see NATURE, 1997, 388, 735).Continuing with this synthesis methodology utilizing ethylene glycolsolvent and matching the amines to framework charge densities for R(M²⁺_(x)Al_(1-x))PO₄, such that 0.4≤x≤0.5, (M²⁺+Mg²⁺, Mn²⁺, Zn²⁺, Co²⁺) thelarge pore materials UCSB-6, -8 and -10 were isolated (see SCIENCE,1997, 278, 2080). Crystal dimensions isolated from that work were oftenon the order of hundreds of microns. Similarly, this approach alsoyielded MeAPO analogs of zeolite rho of the composition where RM²⁺_(0.5)Al_(0.5)PO₄, where R=N, N′-diisopropyl-1,3-propanediamine,M²⁺=Mg²⁺, Co²⁺ and Mn²⁺. The reliance of this synthesis approach on anethylene glycol solvent does not lend itself well to industrial scale,from both a safety and environmental point of view. While several othersembraced Stucky's approach, there has been little activity in thisintermediate charge density region, where 0.2≤x≤0.9 for the [M²⁺_(x)Al_(1-x)PO_(4]) ^(x−) compositions.

Pursuing aqueous chemistry, Wright et al. used highly chargedtriquaternary ammonium SDAs to make new MeAPO materials (see CHEM.MATER., 1999, 11, 2456-2462). One of these materials, STA-5 with the BPHtopology, (Mg_(2.1)Al_(11.9)P₁₄O₂₈), exhibited significant substitutionof Mg²⁺ for Al³⁺, up to about 15%, but less substitution than seen inStucky's non-aqueous ethylene glycol approach.

More recently, Lewis et al. developed aqueous solution chemistry usingquaternary ammonium cations leading to high charge density SAPO, MeAPO,and MeAPSO materials, enabling greater substitution of SiO_(4/2) and[M²⁺O_(4/2)]²⁻ into the framework for [PO_(4/2)]⁺ and [AlO_(4/2)]⁻,respectively, using the ethyltrimethylammonium (ETMA⁺) anddiethyldimethylammonium (DEDMA⁺) SDAs. These materials include ZnAPO-57(U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No. 8,871,177), ZnAPO-67(U.S. Pat. No. 8,697,927) and MeAPSO-64 (U.S. Pat. No. 8,696,886). Therelationship between the increasing product charge densities andreaction parameters, namely the ETMAOH(DEDMAOH)/H₃PO₄ ratios, wereoutlined in the literature (see MICROPOROUS AND MESOPOROUS MATERIALS,189, 2014, 49-63). For the MeAPO compositions, the incorporation of M²⁺observed in these systems was such that for the formulation [M²⁺_(x)Al_(1-x)PO₄]^(x−), x˜0.3.

Applicants have now synthesized a new family of highly chargedmetallophosphate framework materials, designated PST-17, with highercharge densities than the MeAPOs of U.S. Pat. No. 4,567,029 and theZnAPO materials isolated by Lewis. These metallophosphates are preparedfrom aqueous solution utilizing a combination quaternary ammonium andalkali cations. The PST-17 materials have the BPH topology (see DATABASEOF ZEOLITE STRUCTURES, www.iza-structure.org/databases) and have muchhigher metal content than the magnesioaluminophosphate STA-5(Mg_(2.1)A_(111.9)P₁₄O₂₈), the above mentioned MeAPO that has the BPHtopology (see CHEM. MATER., 1999, 11, 2456-2462.) The utility of alkaliin MeAPO-based systems is uncommon and in combination with quaternaryammonium cations under the right conditions enables this system toachieve the charge densities and desired midrange compositions betweenthe low charge density MeAPO and high charge density M²⁺-phosphateextremes.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family ofmetallophosphate molecular sieves designated PST-17. Accordingly, oneembodiment of the invention is a microporous crystalline material havinga three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:

R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z)

where R is at least one quaternary ammonium cation selected from thegroup consisting of ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixturesthereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, Mis a divalent element selected from the group of Zn, Mg, Co, Mn andmixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 toabout 0.9, E is a trivalent element selected from the group consistingof aluminum and gallium and mixtures thereof, “y” is the mole ratio of Eto P and varies from 0.1 to about 0.8 and “z” is the mole ratio of 0 toP and has a value determined by the equation:

z=(m+p⋅r+2⋅x+3⋅y+5)/2

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table A:

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.635.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.583.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.133.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.032.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

Another embodiment of the invention is a process for preparing thecrystalline metallophosphate molecular sieve described above. Theprocess comprises forming a reaction mixture containing reactive sourcesof R, A, M, E and P and heating the reaction mixture at a temperature ofabout 60° C. to about 200° C. for a time sufficient to form themolecular sieve, the reaction mixture having a composition expressed interms of mole ratios of the oxides of:

aR_(2/p)O:bA₂O:cMO:E₂O₃:dP₂O₅:eH₂O

where “a” has a value of about 2.1 to about 100, “b” has a value ofabout 0.1 to about 8.0, “c” has a value of about 0.25 to about 8, “d”has a value of about 1.69 to about 25, and “e” has a value from 30 to5000.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described molecular sieve as a catalyst. Theprocess comprises contacting at least one hydrocarbon with the molecularsieve at conversion conditions to generate at least one convertedhydrocarbon.

Still another embodiment of the invention is a separation process usingthe crystalline PST-17 material. The process may involve separatingmixtures of molecular species or removing contaminants by contacting afluid with the PST-17 molecular sieve. Separation of molecular speciescan be based either on the molecular size (kinetic diameter) or on thedegree of polarity of the molecular species. Removing contaminants maybe by ion exchange with the molecular sieve.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family of high charge density crystallinemicroporous metallophosphate compositions with the BPH topology,designated PST-17. Compared to other early MeAPO materials, the PST-17family of materials contains much more M²⁺and exhibits high framework(FW) charge densities that unlike the other MeAPOs, use of alkalications in addition to organoammonium ions is necessary to balance theFW charge. The instant microporous crystalline material (PST-17) has anempirical composition in the as-synthesized form and on an anhydrousbasis expressed by the empirical formula:

R^(p+) _(r)A⁺ _(m)M^(3°) _(x)E_(y)PO_(z)

where A is at least one alkali cation and is selected from the group ofalkali metals. Specific examples of the A cations include but are notlimited to lithium, sodium, potassium, rubidium, cesium and mixturesthereof. R is at least one quaternary ammonium cation, examples of whichinclude but are not limited to ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA), tetrapropylammonium (TPA⁺) and mixturesthereof, and “r” is the mole ratio of R to P and varies from about 0.1to about 1.0, while “p” is the weighted average valence of R and variesfrom about 1 to 2. M and E are tetrahedrally coordinated and in theframework, M is a divalent element selected from the group of Zn, Mg,Co, Mn and mixtures thereof, while E is a trivalent element selectedfrom aluminum and gallium and mixtures thereof. The value of “m” is themole ratio of A to P and varies from 0.1 to about 1.0, “x” is mole ratioof M to P and varies from 0.2 to about 0.9, while the ratio of E to P isrepresented by “y” which varies from about 0.10 to about 0.8. Lastly,“z” is the mole ratio of O to P and is given by the equation:

z=(m+p⋅r+2⋅x+3⋅y+5)/2.

When only one type of R organoammonium cation is present, then theweighted average valence is just the valence of that cation, e.g., +1 or+2. When more than one R cation is present, the total amount of R isgiven by the equation:

R _(r) ^(p+) =R _(r1) ^((p1)+) +R _(r2) ^((p2)+) +R _(r2) ^((p3)+)+ . ..

the weighted average valence “p” is given by:

$p = \frac{{r\; {1 \cdot p}\; 1} + {r\; {2 \cdot p}\; 2} + {r\; {3 \cdot p}\; 3} + \ldots}{{r\; 1} + {r\; 2} + {r\; 3} + \ldots}$

It has also been noted that in the PST-17 materials of this inventionthat a portion of

M²⁺ may also reside in the pores, likely in a charge balancing role.

The microporous crystalline metallophosphate PST-17 is prepared by ahydrothermal crystallization of a reaction mixture prepared by combiningreactive sources of R, A, E, phosphorous and M. A preferred form of thePST-17 materials is when E is Al. The sources of aluminum include butare not limited to aluminum alkoxides, precipitated aluminas, aluminummetal, aluminum hydroxide, aluminum salts, alkali aluminates and aluminasols. Specific examples of aluminum alkoxides include, but are notlimited to aluminum ortho sec-butoxide and aluminum ortho isopropoxide.Sources of phosphorus include, but are not limited to, orthophosphoricacid, phosphorus pentoxide, and ammonium dihydrogen phosphate. Sourcesof M include but are not limited to zinc acetate, zinc chloride, cobaltacetate, cobalt chloride, magnesium acetate, magnesium nitrate,manganese sulfate, manganese acetate and manganese nitrate. Sources ofthe other E elements include but are not limited to precipitated galliumhydroxide, gallium chloride, gallium sulfate or gallium nitrate. Sourcesof the A metals include the halide salts, nitrate salts, hydroxidesalts, acetate salts, and sulfate salts of the respective alkali metals.R is at least one quaternary ammonium cation selected from the groupconsisting of ETMA⁺, DEDMA⁺, HM²⁺, choline, trimethylpropylammonium,trimethylisopropylammonium, trimethylbutylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA), tetrapropylammonium (TPA⁺) andmixtures thereof, and the sources include the hydroxide, chloride,bromide, iodide and fluoride compounds. Specific examples includewithout limitation ethyltrimethylammonium hydroxide,ethyltrimethylammonium chloride, diethyldimethylammonium bromide,diethyldimethylammonium hydroxide, hexamethonium dihydroxide,hexamethonium dichloride, choline hydroxide, choline chloride,trimethylisopropylammonium hydroxide, propyltrimethylammonium chlorideand tetramethylammonium chloride. In one embodiment R is ETMA⁺. Inanother embodiment, R is diethyldimethylammonium. In yet anotherembodiment, R is trimethylisopropylammonium. Finally, R may also be acombination of ETMA⁺and at least one organoammonium cation selected fromthe group consisting of choline, DEDMA⁺, TMA⁺, HM²⁺,trimethylpropylammonium, trimethylisopropylammonium,trimethylbutylammonium, TEA⁺, and TPA⁺.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aR_(2/p)O:bA₂O:cMO:E₂O₃:dP₂O₅:eH₂O

where “a” varies from about 2.1 to about 100, “b” varies from about 0.1to about 8, “c” varies from about 0.25 to about 8, “d” varies from about1.69 to about 25, and “e” varies from 30 to 5000. If alkoxides are used,it is preferred to include a distillation or evaporative step to removethe alcohol hydrolysis products. The reaction mixture is now reacted ata temperature of about 60° C. to about 200° C. and preferably from about125° C. to about 175° C. for a period of about 1 day to about 3 weeksand preferably for a time of about 1 day to about 7 days in a sealedreaction vessel at autogenous pressure. After crystallization iscomplete, the solid product is isolated from the heterogeneous mixtureby means such as filtration or centrifugation, and then washed withdeionized water and dried in air at ambient temperature up to about 100°C. PST-17 seeds can optionally be added to the reaction mixture in orderto accelerate or otherwise enhance the formation of the desiredmicroporous composition.

The PST-17 metallophosphate-based material, which is obtained from theabove-described process, is characterized by the x-ray diffractionpattern, having at least the d-spacings and relative intensities setforth in Table A below.

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83m-vs 13.34-12.95 6.63-6.83 w 13.68-13.3  6.47-6.65 w-m 14.95-14.635.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m20.45-19.89 4.34-4.46 w-m 21.50-20.98 4.13-4.23 w-m 24.03-23.583.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.133.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.032.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

The PST-17 may be modified in many ways to tailor it for use in aparticular application. Modifications include calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4 in U.S. Pat. No. 6,776,975 which is incorporatedby reference in its entirety. In addition, properties that may bemodified include porosity, adsorption, framework composition, acidity,thermal stability, ion-exchange capacity, etc.

As synthesized, the PST-17 material will contain some of theexchangeable or charge balancing cations in its pores. Theseexchangeable cations can be exchanged for other cations, or in the caseof organic cations, they can be removed by heating under controlledconditions. Because PST-17 is a large pore material, the BPH structurehas 12-ring pores along the c-axis, many organic cations may be removeddirectly by ion-exchange, heating may not be necessary. A preferredmethod of removing organic cations from the pores is ammoniacalcination. Calcination in air converts the organic cations in thepores to protons, which can lead to the loss of some metal, for exampleA1, from the framework upon exposure to ambient atmospheric water vapor.When the calcination is carried out in an ammonia atmosphere, theorganic cation in the pore is replaced by NH4⁺ cation and the frameworkremains intact (see STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p.1324-1331). Typical conditions for ammonia calcinations include the useof gaseous anhydrous ammonia flowing at a rate of 1.1 Umin while rampingthe sample temperature at 5° C./min to 500° C. and holding at thattemperature for a time ranging from 5 minutes to an hour. The resultingammonium/alkali form of PST-17 has essentially the diffraction patternof Table A. Once in this form, the ammonia calcined material may beion-exchanged with H⁺, NH4⁺, alkali metals, alkaline earth metals,transition metals, rare earth metals, or any mixture thereof, to achievea wide variety of compositions with the PST-17 framework in superiorcondition.

When PST-17 or its modified forms are calcined in air, there can be aloss of metal from the framework, such as Al, which can alter the x-raydiffraction pattern from that observed for the as-synthesized PST-17(see STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p.1324-1331). Typicalconditions for the calcination of the PST-17 sample include ramping thetemperature from room temperature to a calcination temperature of 400°to 600° C., preferably a calcination temperature of 450° to 550° C. at aramp rate of 1 to 5° C./min, preferably a ramp rate of 2 to 4° C./min,the temperature ramp conducted in an atmosphere consisting either offlowing nitrogen or flowing clean dry air, preferably an atmosphere offlowing nitrogen. Once at the desired calcination temperature, if thecalcination atmosphere employed during the temperature ramp is flowingclean dry air, it may remain flowing clean dry air. If the calcinationatmosphere during the ramp was flowing nitrogen, it may remain flowingnitrogen at the calcination temperature or it may be immediatelyconverted to clean dry air; preferably at the calcination temperaturethe calcination atmosphere will remain flowing nitrogen for a period of1-10 hours and preferably for a period of 2-4 hours before convertingthe calcination atmosphere to flowing clean dry air. The final step ofthe calcination is a dwell at the calcination temperature in clean dryair. Whether the calcination atmosphere during the initial temperatureramp was flowing nitrogen or flowing clean dry air, once at thecalcination temperature and once the calcination atmosphere is clean dryair, the PST-17 sample will spend a period of 1-24 hours and preferablya period of 2-6 hours under these conditions to complete the calcinationprocess.

The crystalline PST-17 materials of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies.

The PST-17 compositions of this invention can also be used as a catalystor catalyst support in various hydrocarbon conversion processes.Hydrocarbon conversion processes are well known in the art and includecracking, hydrocracking, alkylation of both aromatics and isoparaffin,isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol toolefins, methanation and syngas shift process. Specific reactionconditions and the types of feeds which can be used in these processesare set forth in U.S. Pat. No. 4,310,440, U.S. Pat. No. 4,440,871 andU.S. Pat. No. 5,126,308, which are incorporated by reference. Preferredhydrocarbon conversion processes are those in which hydrogen is acomponent such as hydrotreating or hydrofining, hydrogenation,hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204-649° C.), preferably between 600° and 950° F.(316-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig(1379 to 20,685 kPa g). Contact times usually correspond to liquidhourly space velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15hr⁻¹, preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulationrates are in the range of 1,000 to 50,000 standard cubic feet (scf) perbarrel of charge (178-8,888 std. m³/m³), preferably between 2,000 and30,000 scf per barrel of charge (355-5,333 std. m³/m³). Suitablehydrotreating conditions are generally within the broad ranges ofhydrocracking conditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the PST-17composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (455° C. to593° C.), LHSV values of 0.5 hr⁻¹ to 10 hr⁻¹ and pressure conditions offrom about 0 to 50 psig (0-345 kPa) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic: olefin(e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. andpressures of about 200 to about 1000 psig (1,379 to 6,895 kPa). Furtherdetails on apparatus may be found in U.S. Pat. No. 4,870,222 which isincorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,894 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 hr⁻¹ to about 120 hr⁻¹.Details on paraffin alkylation may be found in U.S. Pat. No. 5,157,196and U.S. Pat. No. 5,157,197, which are incorporated by reference.

The conversion of methanol to olefins is effected by contacting themethanol with the PST-17 catalyst at conversion conditions, therebyforming the desired olefins. The methanol can be in the liquid or vaporphase with the vapor phase being preferred. Contacting the methanol withthe PST-17 catalyst can be done in a continuous mode or a batch modewith a continuous mode being preferred. The amount of time that themethanol is in contact with the PST-17 catalyst must be sufficient toconvert the methanol to the desired light olefin products. When theprocess is carried out in a batch process, the contact time varies fromabout 0.001 hour to about 1 hour and preferably from about 0.01 hour toabout 1.0 hour. The longer contact times are used at lower temperatureswhile shorter times are used at higher temperatures. Further, when theprocess is carried out in a continuous mode, the Weight Hourly SpaceVelocity (WHSV) based on methanol can vary from about 1 hr⁻¹ to about1000 hr⁻¹ and preferably from about 1 hr⁻¹ to about 100 hr⁻¹.

Generally, the process must be carried out at elevated temperatures inorder to form light olefins at a fast enough rate. Thus, the processshould be carried out at a temperature of about 300° C. to about 600°C., preferably from about 400° C. to about 550° C. and most preferablyfrom about 450° C. to about 525° C. The process may be carried out overa wide range of pressure including autogenous pressure. Thus, thepressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig)and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluentin order to more efficiently convert the methanol to olefins. Examplesof the diluents which may be used are helium, argon, nitrogen, carbonmonoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixturesthereof. The amount of diluent used can vary considerably and is usuallyfrom about 5 to about 90 mole percent of the feedstock and preferablyfrom about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well knowncatalyst reaction apparatus known in the art. Thus, a single reactionzone or a number of zones arranged in series or parallel may be used. Insuch reaction zones the methanol feedstock is flowed through a bedcontaining the PST-17 catalyst. When multiple reaction zones are used,one or more PST-17 catalysts may be used in series to produce thedesired product mixture. Instead of a fixed bed, a dynamic bed system,e. g., fluidized or moving, may be used. Such a dynamic system wouldfacilitate any regeneration of the PST-17 catalyst that may be required.If regeneration is required, the PST-17 catalyst can be continuouslyintroduced as a moving bed to a regeneration zone where it can beregenerated by means such as oxidation in an oxygen containingatmosphere to remove carbonaceous materials.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims. The products of thisinvention are designated with the general name PST-17, with theunderstanding that all of the PST-17 materials exhibit a structure withthe BPH topology.

The structure of the PST-17 compositions of this invention wasdetermined by x-ray analysis. The x-ray patterns presented in thefollowing examples were obtained using standard x-ray powder diffractiontechniques. The radiation source was a high-intensity, x-ray tubeoperated at 45 kV and 35 mA. The diffraction pattern from the copperK-alpha radiation was obtained by appropriate computer based techniques.Flat compressed powder samples were continuously scanned at 2° to 56°(2θ). Interplanar spacings (d) in Angstrom units were obtained from theposition of the diffraction peaks expressed as θ where θ is the Braggangle as observed from digitized data. Intensities were determined fromthe integrated area of diffraction peaks after subtracting background,“I₀” being the intensity of the strongest line or peak, and “I” beingthe intensity of each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I₀, the above designations are defined as:

-   -   w=0-15; m=15-60: s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

Example 1

A Teflon beaker was charged with 150.00 g ethyltrimethylammoniumhydroxide (ETMAOH, 20%, SACHEM, Inc.) and placed under a high speedstirring apparatus. Pre-ground aluminum isopropoxide (13.3% Al), 4.82 g,was added to the reaction mixture and dissolved with stirring. This wasfollowed by the dropwise addition of 16.31 g H₃PO₄ (85.7%). Separately,5.22 g Zn(OAc)₂*2H₂O was dissolved in 20.50 g de-ionized water and theresulting solution was added to the reaction mixture in a dropwisefashion. After completion of the addition, the reaction mixture washomogenized for an hour. Then, a solution was prepared by dissolving1.17 g KOAc (99.4%) in 10.00 g de-ionized water. This was added to thereaction mixture in a dropwise fashion and the reaction mixture washomogenized for an additional 20 minutes post-addition. The reactionmixture was distributed among 7 Teflon-lined autoclaves and digested atautogenous pressures at temperatures of 95°, 125°, 150°, and 175° C.,for either 40 or 167 hours or both. The solid products were isolated bycentrifugation and washed with de-ionized water. All of the productswere identified as PST-17 by powder x-ray diffraction, except for theproduct 175° C./167 hour digestion, which also contained a significantimpurity. The representative diffraction lines of which are shown inTable 1 below for the sample from the 125° C./167 hour digestion.Elemental analysis of this same product showed it was composed of theelemental ratios Al/P=0.31, Zn/P=0.70, K/P=0.37, and N/P=0.21,consistent with the stoichiometryETMA_(0.21)K_(0.37)Zn_(0.70)Al_(0.31)P.

TABLE 1 2-Θ d(Å) I/I₀ (%) 6.69 13.19 vs 7.54 11.72 m 13.10 6.76 w 13.406.60 w 14.701 6.02 w 15.39 5.75 w 18.76 4.73 w 20.14 4.41 m 21.14 4.20 m23.75 3.74 w 24.08 3.69 m 26.50 3.36 w 27.20 3.28 w 27.43 3.25 w 28.263.16 w 28.56 3.12 w 29.66 3.01 m 30.08 2.97 m 30.52 2.93 w 31.06 2.88 w31.26 2.86 w 33.31 2.69 w 33.82 2.65 w 34.25 2.62 w 35.08 2.56 w 35.742.51 w 36.48 2.46 w 38.02 2.36 w 38.85 2.32 w 39.21 2.30 w 39.72 2.27 w40.76 2.21 w 42.98 2.10 w 43.42 2.08 w 47.37 1.92 w 48.84 1.86 w 49.541.84 w 50.14 1.82 w 51.10 1.79 w 53.06 1.72 w 53.38 1.72 w 53.96 1.70 w55.60 1.65 w

Example 2

A Teflon beaker was charged with 174.00 g Diethyldimethylammoniumhydroxide (DEDMAOH, 20% aqueous, SACHEM, Inc.) and placed under a highspeed mixer. Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g, wasadded to the reaction mixture and stirred until dissolved. This wasfollowed by the dropwise addition of 16.69 g H₃PO₄ (85.7%). Separately,Zn(OAc)₂*2H₂O, 5.34 g, was dissolved in 25.00 g de-ionized water. Thissolution was added dropwise to the reaction mixture with vigorousstirring to homogenize. An additional solution was prepared bydissolving KOAc (99.4%), 1.19 g, in 12.88 g de-ionized water. Thissolution was added dropwise to the reaction mixture and stirred for anhour. The reaction mixture was distributed among 7 Teflon-linedautoclaves and digested at autogenous pressures at temperatures of 95°,125°, 150°, and 175° C., for either 48, 136 hr, or 170 hours. The solidproducts were isolated by centrifugation and washed with de-ionizedwater. With the exception of the product of the 95° C./170 hourdigestion, all of the products were found to contain PST-17 by powderx-ray diffraction. The representative diffraction lines are shown inTable 2 below for the PST-17 products from the 125° C./48 hour (Table2a) and 175° C./136 hour (Table 2b) digestions. Elemental analysis ofthese same products showed they were composed of the following elementalratios, 125° C./48 hr: Al/P=0.36, Zn/P=0.75, K/P=0.36, and N/P=0.25,consistent with the stoichiometryDEDMA_(0.25)K_(0.36)Zn_(0.75)Al_(0.36)P and 175° C./136 hr: Al/P=0.39,Zn/P=0.60, K/P=0.26, and N/P=0.31, consistent with the stoichiometryDEDMA_(0.31)K_(0.26)Zn_(0.60)Al_(0.39)P.

TABLE 2 Table 2a Table 2b 2-Θ d(Å) I/I₀ (%) 2-Θ d(Å) I/I₀ (%) 6.70 13.19vs 6.72 13.14 s 7.54 11.72 s 7.56 11.69 vs 13.06 6.77 w 10.11 8.75 w13.40 6.60 w 13.11 6.75 w 14.71 6.02 w 13.44 6.58 w 15.40 5.75 m 14.746.01 w 18.76 4.73 m 15.44 5.74 m 20.02 4.43 w 16.56 5.35 w 20.18 4.40 m18.76 4.72 m 21.12 4.20 m 20.22 4.39 m 23.73 3.75 w 21.18 4.19 m 24.123.69 m 23.78 3.74 w 26.32 3.38 w 24.18 3.68 m 26.48 3.36 w 26.54 3.36 m27.18 3.28 w 27.24 3.27 m 27.42 3.25 w 27.44 3.25 w 28.24 3.16 w 28.283.15 m 28.56 3.12 w 28.64 3.11 m 29.64 3.01 m 29.70 3.01 m 30.12 2.96 m30.18 2.96 m 30.58 2.92 m 30.64 2.92 m 31.08 2.88 w 31.20 2.86 w 31.222.86 w 33.36 2.68 m 33.28 2.69 w 33.90 2.64 m 33.84 2.65 m 34.36 2.61 w34.27 2.61 w 35.14 2.55 w 35.04 2.56 w 35.73 2.51 w 35.72 2.51 w 36.082.49 w 36.50 2.46 w 36.58 2.45 w 38.09 2.36 w 38.14 2.36 w 39.22 2.30 w38.93 2.31 w 39.72 2.27 w 39.82 2.26 w 39.96 2.25 w 40.84 2.21 w 40.782.21 w 42.97 2.10 w 41.29 2.18 w 43.54 2.08 w 42.92 2.11 w 44.10 2.05 w43.46 2.08 w 44.33 2.04 w 44.20 2.05 w 47.53 1.91 w 46.45 1.95 w 48.381.88 w 48.88 1.86 w 48.98 1.86 w 49.52 1.84 w 49.56 1.84 w 50.18 1.82 w50.33 1.81 w 51.04 1.79 w 51.14 1.78 w 53.02 1.73 w 53.12 1.72 w 53.371.72 w 53.48 1.71 w 53.93 1.70 w 54.10 1.69 w 55.24 1.66 w 55.30 1.66 w55.69 1.65 w

Example 3

A Teflon bottle was charged with 159.12 g ETMAOH (20%) followed by theaddition of 6.31 g of Al-isopropoxide (Al(OiPr)₃, 98+%). The mixture wasstirred in a sealed bottle until the Al(OiPr)₃ was fully dissolved. Themixture was transferred to a Teflon beaker equipped with an overheadhigh speed stirrer. Then, H₃PO₄ (85%), 20.95 g, was added slowly withvigorous mixing. Separately, 6.78 g Zn acetate dihydrate was dissolvedin 30 g deionized water. The Zn solution was then slowly added to theAl/P/ETMAOH solution over a period of 30 minutes while mixing continued.Homogenization of the reaction mixture was continued for 30 minutesafter completion of the Zn addition. In a separate beaker, 1.82 g KBrwas dissolved in 25.03 g deionized water. This was then added slowly tothe reaction mixture while continuing to mix. Again, mixing wascontinued for 30 minutes after this addition was completed. A clearsolution reaction mixture was then distributed between 4×125 mlautoclaves and digested for 7 and 8 d at 150° C. The solid products wereisolated by centrifugation and washed with de-ionized water. PowderX-ray diffraction showed all of the products to be PST-17 with the BPHtopology. Representative diffraction lines for the PST-17 product aregiven in Table 3 below.

TABLE 3 2Θ d(Å) I/I₀ % 6.83 12.94 vs 7.69 11.49 m 10.24 8.63 w 13.246.68 w 13.55 6.53 w 14.87 5.95 w 15.55 5.70 w 18.92 4.69 w 20.30 4.37 w21.32 4.16 w 23.91 3.72 w 24.27 3.66 m 26.66 3.34 w 27.38 3.25 w 27.603.23 w 28.46 3.13 w 28.76 3.10 w 29.84 2.99 w 30.26 2.95 m 30.77 2.90 w31.27 2.86 w 31.43 2.84 w 33.51 2.67 w 34.02 2.63 w 35.26 2.54 w 36.682.45 w 38.24 2.35 w 39.85 2.26 w 40.14 2.24 w 40.97 2.20 w 43.22 2.09 w43.62 2.07 w

Example 4 Na⁺ Ion-Exchange of PST-17

A Na⁺ ion-exchange was carried out on the product from the 7 d at 150°C. reaction in Example 3. A 1.75 g portion of the dried PST-17 wasslurried in 29.2 g of a 6% NaCl solution. The slurry was covered andheated to 75° C. while mixing on a stir plate. The slurry was held at75° C. for about 1 hour. The solid was then collected and washed withdeionized water. This process was repeated two additional times. Thesolid was dried at 100° C. after the final exchange step. A Leco CHNanalysis showed that the C level was reduced to 2.75 wt % after theexchange, where typically as-synthesized PST-17 contains 6.5 to 11%carbon. This demonstrates that significant portions of the organiccation may be removed directly by ion-exchange.

Example 5 NH4⁺ Ion-Exchange of PST-17

A Teflon bottle was charged with 891.07 g ETMAOH (20%, SACHEM, Inc.). A35.31 g portion of aluminum isopropoxide (AIP, 98+%) was added and themixture was stirred in the sealed bottle until the AIP was fullydissolved. The reaction mixture was transferred to a Teflon beaker and117.32 g of H₃PO₄ (85%) was added slowly while mixing with an overheadstirrer. Separately, 37.95 g of zinc acetate dehydrate was dissolved in168.00 g of deionized water. The zinc acetate solution was then slowlyadded to the reaction mixture over a period of 2 hours, while mixingwith an overhead stirrer. The mixing was continued for 30 min after theaddition was completed. In a separate beaker, 10.18 g KBr was dissolvedin 25.03 g deionized water. This was then added slowly to the reactionmixture while continuing to mix with an overhead stirrer. The mixing wascontinued for 30 min after this addition was complete. A slightly hazysolution resulted. The solution was then transferred to a 2 L autoclaveand digested for 7 days at 150° C. at autogenous pressure. The productwas isolated by centrifugation, washed with deionized water and dried at100° C. Powder x-ray diffraction showed the product to be PST-17 withthe BPH topology. Representative diffraction lines for the PST-17product are shown in Table 4a below. Elemental analysis showed thePST-17 to consist of the following elemental ratios: Al/P=0.32,Zn/P=0.71, K/P=0.37, and N/P=0.25, consistent with the empirical formulaETMA_(0.25)K_(0.37)Zn_(0.71)Al_(0.32)P. Specifically, the carbon contentin this PST-17 was 7.56%.

A 20 g portion of the as-synthesized PST-17 material was then ammoniumion-exchanged. A 20 g portion of NH₄NO₃ was dissolved in 200 g deionizedwater. The dried PST-17 material was then added to this solution whilemixing on a magnetic stir plate. The slurry was covered and heated to75° C. for 1.5 hours. The solid was collected and washed by filtration.The exchange procedure was repeated two additional times. The solid wasdried at 100° C. after the final exchange step. The ammoniumion-exchanged PST-17 was identified as such by powder x-ray diffraction;the representative diffraction lines shown in Table 4b. Leco CHNanalysis showed that the carbon content in the ammonium ion-exchangedPST-17 is 0.21%, indicating that more than 97% of the ETMA⁺ SDA had beenremoved by ion-exchange.

TABLE 4 Table 4a Table 4b 2-Θ d(Å) I/I₀ % 2-Θ d(Å) I/I₀ % 6.72 13.15 vs6.73 13.12 vs 7.58 11.65 m 7.61 11.61 s 10.13 8.72 w 10.15 8.71 w 13.146.73 w 13.19 6.71 w 13.45 6.58 w 13.46 6.57 m 14.76 6.00 w 14.81 5.98 w15.44 5.73 w 15.47 5.72 w 16.60 5.34 w 18.86 4.70 w 18.82 4.71 w 20.224.39 w 20.20 4.39 w 21.29 4.17 m 21.21 4.18 w 23.89 3.72 w 22.84 3.89 w24.21 3.67 m 24.16 3.68 m 26.63 3.35 w 26.58 3.35 w 27.08 3.29 w 27.273.27 w 27.38 3.25 w 27.51 3.24 w 27.62 3.23 w 28.35 3.15 w 28.44 3.14 w28.63 3.12 w 28.68 3.11 w 29.74 3.00 w 29.82 2.99 m 30.15 2.96 m 30.192.96 m 30.63 2.92 w 30.71 2.91 w 31.34 2.85 w 31.16 2.87 w 33.41 2.68 w31.41 2.85 w 33.90 2.64 w 33.53 2.67 w 35.16 2.55 w 33.96 2.64 w 35.842.50 w 34.23 2.62 w 36.53 2.46 w 34.44 2.60 w 38.12 2.36 w 35.30 2.54 w38.93 2.31 w 36.60 2.45 w 39.34 2.29 w 38.21 2.35 w 39.78 2.26 w 39.832.26 w 40.85 2.21 w 40.93 2.20 w 43.07 2.10 w 43.19 2.09 w 43.48 2.08 w43.58 2.07 w 44.25 2.05 w 46.14 1.97 w 46.02 1.97 w 49.77 1.83 w 46.571.95 w 51.36 1.78 w 48.97 1.86 w 53.32 1.72 w 49.62 1.84 w 55.70 1.65 w50.21 1.82 w 50.66 1.80 w 51.18 1.78 w 51.69 1.77 w 53.15 1.72 w 53.441.71 w 54.04 1.70 w

Specific Embodiments

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a microporous crystallinemetallophosphate material having a three-dimensional framework ofM²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and anempirical composition in the as synthesized form and anhydrous basisexpressed by an empirical formula of R^(p+) _(r)A⁺ _(m)M²⁺_(x)E_(y)PO_(z) where R is at least one quaternary ammonium cationselected from the group consisting of ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal selected from the group consisting of Li⁺, Na⁺,K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to Pand varies from 0.1 to 1.0, M is a divalent element selected from thegroup of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of Mto P and varies from 0.2 to about 0.9, E is a trivalent element selectedfrom the group consisting of aluminum and gallium and mixtures thereof,“y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z”is the mole ratio of O to P and has a value determined by the equationz=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.635.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.583.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.133.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.032.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwhere in the metallophosphate material A is potassium. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the first embodiment in this paragraph where in themetallophosphate material R is ethyltrimethylammonium cation, ETMA⁺. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the first embodiment in this paragraph wherein the metallophosphate material R is the diethyldimethylammoniumcation, DEDMA⁺. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the first embodiment inthis paragraph where in the metallophosphate material R is thetrimethylisopropylammonium cation. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph where a crystalline modified form ofthe crystalline microporous metallophosphate comprises athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and derived by modifying the crystallinemicroporous metallophosphate, the modifications comprising calcination,ammonia calcinations, ion-exchange, steaming, various acid extractions,ammonium hexafluorosilicate treatment, or any combination thereof.

A second embodiment of the invention is a method for preparing amicroporous crystalline metallophosphate material having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and anhydrous basis expressed by an empirical formulaof R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least onequaternary ammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium,trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.1 to about 1.0, “p” is the weighted average valence of R andvaries from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of O to P and has avalue determined by the equation z=(m+p⋅r+2⋅x+3⋅y+5)/2 and ischaracterized in that it has the x-ray diffraction pattern having atleast the d-spacings and intensities set forth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.635.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.583.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.133.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.032.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 wthe process comprising forming a reaction mixture containing reactivesources of R, A, E, M and P, and heating the reaction mixture at atemperature of about 60° C. to about 200° C. for a time sufficient toform the metallophosphate molecular sieve, the reaction mixture having acomposition expressed in terms of mole ratios of the oxides of aR_(2/p)ObA₂O cMO E₂O₃ dP₂O₅ eH₂O where “a” has a value of about 2.1 to about100, “b” has a value of about 0.1 to about 8.0, “c” has a value of about0.25 to about 8, “d” has a value of about 1.69 to about 25, and “e” hasa value from 30 to 5000. An embodiment of the invention is one, any orall of prior embodiments in this paragraph up through the secondembodiment in this paragraph where the initial reaction mixture is aclear solution before digestion. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the secondembodiment in this paragraph where A is selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺and mixtures thereof and thesource of A is selected from the group consisting of halide salts,nitrate salts, acetate salts, sulfate salts, hydroxide salts andmixtures thereof. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the second embodiment inthis paragraph where M is selected from the group consisting of Zn²⁺,Mn²⁺, Co²⁺ and Mg²⁺ and mixtures thereof and where the source of M isselected from the group consisting of halide salts, nitrate salts,acetate salts, sulfate salts and mixtures thereof. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph where the source of E isselected from the group consisting of aluminum isopropoxide, aluminumsec-butoxide, precipitated alumina, Al(OH)₃, alkali aluminate salts,aluminum metal, aluminum halide salts, aluminum sulfate salts, aluminumnitrate salts, precipitated gallium oxyhydroxide, gallium nitrate,gallium sulfate and mixtures thereof. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thesecond embodiment in this paragraph where the reaction mixture isreacted at a temperature of about 125° C. to about 185° C. for a time ofabout 1 day to about 14 days. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph where R is ethyltrimethylammonium, ETMA⁺.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphwhere R is diethyldimethylammonium, DEDMA⁺. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph further comprisingadding PST-17 seeds to the reaction mixture.

A third embodiment of the invention is a hydrocarbon conversion processcomprising contacting a hydrocarbon stream with a catalyst athydrocarbon conversion conditions to generate at least one convertedproduct, wherein the catalyst is selected from the group consisting of acrystalline microporous PST-17 material, a modified crystallinemicroporous PST-17 material and mixtures thereof, where PST-17 is acrystalline microporous metallophosphate having a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedralunits and an empirical composition in the as synthesized form andanhydrous basis expressed by an empirical formula of R^(p+) _(r)A⁺_(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammoniumcation selected from the group consisting of ethyltrimethylammonium(ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal such as Li^(t), Na⁺, K⁺, Rb⁺ and Cs⁺ andmixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mnand mixtures thereof, “x” is the mole ratio of M to P and varies from0.2 to about 0.9, E is a trivalent element selected from the groupconsisting of aluminum and gallium and mixtures thereof, “y” is the moleratio of E to P and varies from 0.1 to about 0.8 and “z” is the moleratio of O to P and has a value determined by the equationz=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.635.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.583.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.133.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.032.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 wand the modified crystalline microporous PST-17 consists of athree-dimensional framework of [M^(2+O) _(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units derived from PST-17 via the modificationprocesses of calcination, ammonia calcinations, ion-exchange, steaming,various acid extractions, ammonium hexafluorosilicate treatment, or anycombination thereof. An embodiment of the invention is one, any or allof prior embodiments in this paragraph up through the third embodimentin this paragraph wherein the hydrocarbon conversion process is selectedfrom the group consisting of cracking, hydrocracking, alkylation,isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrofining, hydrodenitrogenation, hydrodesulfurization,methanol to olefins, methanation, syngas shift process, olefindimerization, oligomerization, dewaxing, and combinations thereof.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

1. A microporous crystalline metallophosphate material having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and anhydrous basis expressed by an empirical formulaof:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium,trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.1 to about 1.0, “p” is the weighted average valence of R andvaries from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of O to P and has avalue determined by the equation:z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.674.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386 3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.5052.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w


2. The metallophosphate material of claim 1 where A is potassium.
 3. Themetallophosphate material of claim 1 where E is aluminum. Themetallophosphate material of claim 1 where R is ethyltrimethylammoniumcation, ETMA⁺.
 5. The metallophosphate material of claim 1 where R isthe diethyldimethylammonium cation, DEDMA⁺.
 6. The metallophosphatematerial of claim 1 where R is the trimethylisopropylammonium cation. 7.A crystalline modified form of the crystalline microporousmetallophosphate of claim 1, comprising a three-dimensional framework of[M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units andderived by modifying the crystalline microporous metallophosphate ofclaim 1, the modifications comprising calcination, ammonia calcinations,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof.
 8. A methodfor preparing a microporous crystalline metallophosphate material havinga three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and anhydrous basis expressed by an empirical formulaof:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium,trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.1 to about 1.0, “p” is the weighted average valence of R andvaries from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of O to P and has avalue determined by the equation:z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.674.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386 3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.5052.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

the process comprising forming a reaction mixture containing reactivesources of R, A, E, M and P, and heating the reaction mixture at atemperature of about 60° C. to about 200° C. for a time sufficient toform the metallophosphate molecular sieve, the reaction mixture having acomposition expressed in terms of mole ratios of the oxides of:aR_(2/p)O:bA₂O:cMO:E₂O₃:dP₂O₅:eH₂O where “a” has a value of about 2.1 toabout 100, “b” has a value of about 0.1 to about 8.0, “c” has a value ofabout 0.25 to about 8, “d” has a value of about 1.69 to about 25, and“e” has a value from 30 to
 5000. 9. The method of claim 8 where theinitial reaction mixture is a clear solution before digestion.
 10. Themethod of claim 8 where A is selected from the group consisting of Li⁺,Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof and the source of A isselected from the group consisting of halide salts, nitrate salts,acetate salts, sulfate salts, hydroxide salts and mixtures thereof. 11.The method of claim 8 where M is selected from the group consisting ofZn²⁺, Mn²⁺, Co²⁺ and Mg²⁺ and mixtures thereof and where the source of Mis selected from the group consisting of halide salts, nitrate salts,acetate salts, sulfate salts and mixtures thereof.
 12. The method ofclaim 8 where the source of E is selected from the group consisting ofaluminum isopropoxide, aluminum sec-butoxide, precipitated alumina,Al(OH)₃, alkali aluminate salts, aluminum metal, aluminum halide salts,aluminum sulfate salts, aluminum nitrate salts, precipitated galliumoxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof. 13.The method of claim 8 where the reaction mixture is reacted at atemperature of about 125° C. to about 185° C. for a time of about 1 dayto about 14 days.
 14. The method of claim 8 where R isethyltrimethylammonium, ETMA⁺.
 15. The method of claim 8 where R isdiethyldimethylammonium, DEDMA⁺.
 16. The method of claim 8 furthercomprising adding PST-17 seeds to the reaction mixture.
 17. Ahydrocarbon conversion process comprising contacting a hydrocarbonstream with a catalyst at hydrocarbon conversion conditions to generateat least one converted product, wherein the catalyst is selected fromthe group consisting of a crystalline microporous PST-17 material, amodified crystalline microporous PST-17 material and mixtures thereof,where PST-17 is a crystalline microporous metallophosphate having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and anhydrous basis expressed by an empirical formulaof:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM^(2')), choline [Me₃NCH₂CH₂OH]⁺,trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixturesthereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, Mis a divalent element selected from the group of Zn, Mg, Co, Mn andmixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 toabout 0.9, E is a trivalent element selected from the group consistingof aluminum and gallium and mixtures thereof, “y” is the mole ratio of Eto P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O toP and has a value determined by the equation:z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.674.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386 3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.5052.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851 2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

and the modified crystalline microporous PST-17 consists of athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units derived from PST-17 via the modificationprocesses of calcination, ammonia calcinations, ion-exchange, steaming,various acid extractions, ammonium hexafluorosilicate treatment, or anycombination thereof.
 18. The process of claim 17 wherein the hydrocarbonconversion process is selected from the group consisting of cracking,hydrocracking, alkylation, isomerization, polymerization, reforming,hydrogenation, dehydrogenation, transalkylation, dealkylation,hydration, dehydration, hydrotreating, hydrofining,hydrodenitrogenation, hydrodesulfurization, methanol to olefins,methanation, syngas shift process, olefin dimerization, oligomerization,dewaxing, and combinations thereof